Copper films are increasingly employed in semiconductor devices as a replacement for aluminum in the fabrication of electrical conductors. Skilled artisans will appreciate that copper conductors have a variety of benefits including higher conductivity and reduced susceptibility to electromigration (which degrades device reliability). Nevertheless, the application of copper conductors includes certain drawbacks, one of which is a decreased adhesion to dielectric films which are employed to separate conducting paths within the semiconductor devices. The reduced adhesion of copper to certain dielectric materials can lead to new failure mechanisms which reduce the utility of copper conductors, especially as new dielectric materials are introduced in association with advanced semiconductor processing technology.
One method of mitigating the problems associated with copper conducting films is to coat the copper surface or surfaces with an additional material having higher adhesion to dielectric materials. One proposed technique involves the electroless plating of cobalt tungsten phosphide (CoWP) onto the copper film before application of a dielectric film. The electroless plating process involves placing a semiconductor device undergoing fabrication into a plating solution which selectively deposits the CoWP on exposed copper metal only, and does not require any masking steps or application of external electrical currents. The plating solution is a combination of organic and inorganic chemical components which interact to nucleate the desired film and cause its growth so as to produce desired physical and chemical properties such as composition, conductivity, thickness, and grain structure.
In one example of a plating solution for the electroless plating of CoWP, cobalt chloride or cobalt sulfate is employed as a source for cobalt ions, sodium tungstate is employed as a source for tungsten ions, and sodium hypophosphite is employed as a source for phosphorus-containing ions. The organic chemical dimethylamine borane (DMAB) is employed as a reducing agent for reducing the cobalt and tungsten ions. Typically, the DMAB initiates the metal alloy plating on the copper surface. After initiation, further reduction occurs partially by action of the DMAB and by hypophosphite ions, which also participate in the reactions. In conventional electroplating, metal ions in a plating solution receive electrons from an external power supply and are chemically reduced to metallic form. In electroless plating, the reducing electrons are supplied by the chemical reducing agent. A complexing agent such as citric acid may be employed to stabilize metal ions in solution and to reduce the possibility of spontaneous decomposition. Citric acid can further act as a pH adjuster.
During the deposition process, reactants in the plating solution are consumed and waste products may accumulate. In order to ensure that the plating solution constituents remain within desirable concentration levels it is necessary to measure and adjust the component concentrations. One approach, known to those skilled in the art, is to take a sample of the plating bath and perform conventional chemical titrations to determine the concentrations of the plating bath constituents. A disadvantage to this approach is that it is slow and tedious. Another disadvantage is that the titration results in a significant amount of waste generation and a need for supplying additional chemicals needed by the titration process. Finally, the titration process is typically conducted away from the process equipment performing the electroless plating process. Additionally, matrix effects may confound the titration process in which the presence of one chemical component inhibits or alters the quantitative determination of other components.
Articles in trade publications familiar to those skilled in the art have proposed methods for control of electroless plating baths. For example, a cyclic voltametric stripping (CVS) technique has been discussed as a method to analyze organic components in a cobalt tungsten phosphide (CoWP) electroless plating solution. Other articles have also suggested UV-vis spectroscopic techniques for a determination of the concentration of metal ions in a plating solution. Raman spectroscopy has also been given mention as potentially applicable to the monitoring of chemical solutions utilized in electroless plating. Skilled artisans will appreciate that effective utilization of these techniques for plating bath control would benefit from a detailed teaching of how these analytical techniques may be combined and configured.
Specifically, methods are needed for using quantitative results obtained from these systems for the real-time or near real-time control of the plating bath. Further, a means of measurement and control of the plating solution pH in combination with spectroscopic techniques would advance the art. Skilled artisans recognize that pH is a measure of the hydronium ion (H3O+) concentration in solution; pH is approximately equal to log10[H3O+], where [H3O+] is the hydronium ion concentration in moles per liter of solution.
Therefore, what is needed is an improved means for measuring and controlling concentrations of chemical constituents in a plating bath. In particular, a system is needed which combines the capabilities of determining the concentrations of organic constituents and metals in the plating bath, as well as a measure of the pH of the plating bath with methods for altering the plating bath constituent concentrations so as to produce plated films having desirable physical and chemical properties. The measurements should be largely immune from matrix effects and should operate in a comparatively short time interval to enable real-time or near real-time control of the plating bath.